Mineral-oil derivative



UNITED STATES PATENT OFFICE.

HAROLD T. MAIT'LAND, OF MARCUS HOOK, PENNSYLVANIA, ASSIGNOR TO SUN COM- PANY, OF PHILADELPHIA, PENNSYLVANIA, A CORPORATION OF NEW JERSEY.

MINERAL-OIL DERIVATIVE.

No Drawing.

To all whom it may concern.

Be it known that I, HAROLD T. MAITLAND, a citizen of the United States, residing at Marcus Hook, county of Delaware, and State of Pennsylvania, have invented a new and useful Improvement in Mineral-Oil Derivatives, of which the following is a full, clear, and exact description,

The object of my invention is to produce by treating mineral oils, saponifiable oils or organic compounds which will have certain characteristics of animal oils, vegetable oils and resins and which are adapted for various uses, some of the principal of which are for the manufacture of soaps, hydrogenated compounds, greases, drying oils, cutting oils, nitrated, sulphonated and chlorinated compounds, and addition, substitution or condensation products, some of which have antiseptic and medicinal properties.

The derivatives from mineral oil produced by my process have peculiar characteristics which no other known derivatives from mineral oil possess, in that the are both insoluble in water and saponi able, possessing, in the main, when saponified, the qualities of ordinar soaps made from oil of vegetable or animal origin. The products, in the preferred forms in which I have made them, have also the following specific characteristics: They are odorless, they do not become rancid, and when saponified they are miscible in all proportions with water and mineral oil, as hereinafter more particularl explained.

The pro uction from mineral oil of sulfoacids or sulfonic compounds which are saponifiable and when saponified exhibit some of the characteristics of ordinary soap is known. These sulfonated acids, however, are quite different from my novel products both in constitution and in certain essential characteristics. Thus the sulfonated acids, as their name implies contain a large percentage of sulfur, they are soluble in water, and when saponified the do not undergo the process of hydrolytic ecomposition which occurs with ordinary soaps. The sulfur content of my products, on the contrary, is scarcely more than a trace, and exists chiefly in the form of sulfates, which are there as impurities. My products, therefore, are not sulfo-acids or sulfonated compounds in any sense, as they are insoluble in water, and

Specification of Letters Patent.

Patented Aug. 15, 1922.

Application filed April 15, 1919. Serial No. 290,229.

they behave, when saponified, like ordinary soaps in that they undergo the same character of hydrolytic decomposition and exhibit most other, and probably all other, important qualities which characterize ordinarv soaps.

l\ y new products cannot, by reason of their novelty, be too specifically designated. They are, however, saponifiable oils or a series of oils and it is scarcely uestionable that they are organic acids 0 the resin group.

The main advantage of my new products is their cheapness, by reason of the cheapness of mineral oils as compared with animal and vegetable oils. They have, however, not only the economical advantage of being derivatives from mineral oils, but they have the further economical advantage of being derivatives from materials which are byproducts in the manufacture of lubricating oils and other standard refined products 'from crude oils, which by-products have hitherto either been wasted or only partially utilized for the manufacture of products which command a comparativel small price. My products have a muc greater commercial value than lubricating oil itself, making it profitable to so conduct the whole refining process as to make the production of my new products the chief object.

I do not claim herein the process herein described for manufacturing my new prodnot, as the same forms the subject-matter of a separate application filed April 15, 1919, Serial No. 290,227.

While any crude petroleum is possibly or probably adalpted for use in the execution of my process, prefer to use Texas crude oil, or a crude petroleum of that nature on ac count of the particular group of hydrocarbons and their mobility to conversion which are found in an oil of this kind. The yield of saponifiable oil is probably increased by the particular distilling process which I preferably employ to secure" the so-called lubricating oil stock from which both lubricating oil and my new roducts are made, and I shall therefore briefly describe such distilling process; although it will be understood that the essential steps of my process may be practiced starting with any lubricating oil stock or distillate, or at least any lubricating oil stock or distillate made by distilling crude petroleum of the proper grade in the ordinary way.

I first take the crude petroleum and subject it to a preliminary distillation in which all of the crude products is distilled off except a relatively small um. The distillates are then subjected to a second distillation, the heavier product remaining in the still being the stock from which lubricating oil may be made. The second distillate is then redistilled, light oils being distilled off, the part remaining also being adapted for use as lubricating stock.

While some saponifiable compounds may be separated from the mineral oil by treatment with fullers earth or bone char, followed by extraction of the saponifiable compounds from the above mentioned materials with some solvent such'as alcohol, ether, benzol, carbon bisulfide, etc., I prefer to treat them successively with an acid and an alkali, either first treating with an acid and then with an alkali, or the reverse. A certain group of these saponifiable oils may be removed b first precipitating them with an alkali and removing them before treating with sulfuric acid; or I may proceed in the usual way, namely: byfirst treatin the lubricating stock with an acid, pro erably sulfuric acid, with agitation, followed by settlement, for-min the sludge, which is drawn off. If sul uric acid be used, it should not be the anh dride, or even fuming acid, as otherwisesul o-acids will be formed,

which may be difficult or impossible to eliminate, or which may make impossible the production of the water-insoluble organic acid sought. The treatment of the sludge, for the purpose of producing a saponifiable oil or or anic acid having the characteristics herein fore enumerated, is hereinafter set forth. After the sludge is separated from the lubricating stock, the lubrlcating stock is treated with caustic soda or any suitable alkali in the customary wa The precipitate from the alkali treatmen of the lubricating stock which, when drawn off, is usually allowed to run off as waste, is a soap consisting of a sodium salt of the hereinbefore mentioned organic compounds with about sixty per cent of water. I decompose this soap 'with a dilute mineral acid. A seven per cent solution of sulfuric acid has been found quite satisfactory for this work, although certain variable features in the precipitate from the alkali treatment, such as an extraordinary excess of alkali or an excess or scarcity of water, may, to some extent, govern the strength of this solution. The amount of this solution is controlled entirely by conditions existing in the precipitate from the alkali treatment. It is, however, desirable that the amount of percentage of residuwater in this decomposing solution should be sufficient to dissolve and carry away the resultant salts of this reaction. The total amount of water, including the water already present in the precipitate, should approach the total amount of liberated saponifiable oils plus dissolved or suspended mineral oils. The precipitate, which is drawn off, consists chiefly of water containin in solution sodium sulfate, acid sodium sul fate and impurities from the commercial alkali used.

The following more specific example may be given of the practice of the process, starting with the lubricating oil stock and ending with the production of the saponifiable oils or organic acids which remain after drawing off the last named precipitate:

2300 barrels of lubricating stock are thoroughly agitated with approximately 75 barrels of concentrated sulfuric acid (93.5% H SO and caused to settle by appropriate temperature conditions. This mixture of oil and acid separates into three distinct layers.

The top layer A consists of about 2175 barrels of treated lubricating stock, with approximately .75% sulfuric acid in suspension.

The middle layer B is composed of approximately 180 barrels of a mixture of sludge and acid. The lower layer C consists of a small amount of sulfuric acid with some sludge in solution. These layers are successively drawn off.

The to layer A remaining in the agitator is slbwly agitated with about 300 barrels of a weak solution of caustic soda and permitted to settle.

Two layers separate. The top layer D consists. chiefly of treated lubricating oil amounting, approximately, to 1925 barrels. The bottom layer'E is a mixture of lubricating oil, soap and alkaline salt water, amounting to about 550 barrels.

The lower layer E is drawn off and treated by agitation with about 150 barrels of 7% sulfuric acidat approximately 100 (1., which causes the soap to be decomposed. Approximately 150 barrels of hot water are then added and the mixture is agitated and allowed to settle. It readily separates into two layers, the upper layer F consisting of approximately 250 barrels of saponifiable acids with some mineral oil, while the bottom layer G, amounting to about 600 barrels, is the salt water resulting from the above reaction.

After drawing off the bottom layer G, layer F may be saponified with caustic soda or other suitable alkali, making a soap containing very little water. A hot solution of approximately 51BeNaOH has been used with very good results. In order to keep the soap bright, the water content is controlled by the strength of the alkali solution.

Approximately two to seven per cent of water is permitted to remain in the soap, but the quantity of water incorporated is controlled by the product desired.

In many cases. if suflicient care is taken to allow layer E to settle properly, it will separate into three layers, namely: a top layer H, about 18%, consisting chiefly of mineral oil; a middle layer 1, about 39%, consisting of a soap; and a bottom layer J, about 43%, of alkaline salts and water.

A soap made in accordance with the fore going process is adapted for all uses to which soap made from animal or vegetable oils is adapted.

The saponifiable mineral oil derivative made in accordance with the above process hasthe following characteristics: It is, I believe, an organic acid, is a li uid at ordinary temperatures, is water inso uble, is practically odorless, does not become rancid, and has a sulfur content, if the process is properly carried out, as low as about 0.2 per cent, this minute proportion of sulfur probably existing as sulfuric acid or sulfates whose absolutely complete removal has not been effected. It is readily sapouifiable with caustic soda or other suitable alkali and when saponified forms with water a colloidal solution similar to that formed with water by any soap of animal or vegetable origin. The saponified product is not only miscible in all proportions with water and adapted to undergo the Character of hydrolytic decomposition that occurs with ior' dinary soaps, but is also soluble in all proportions with mineral oil and when mixed with mineral oil and water forms a homogeneous emulsion.

Both soaps form with water a colloidal solution similar to that formed with water by any soap of animal or vegetable origin. This solution with Water of the second saponified product, upon drying, partially hydrolyzes and does not readily dissolve in water the second time, making an ideal road oil or dust preventative. The first product, when saponitied, is soluble in all propor tions with mineral oil. The second product, when saponified, is partially soluble in mineral oil, the degree of its solubility depending upon the character of the oil. Both soaps, when mixed with mineral oil and water, form homogeneous emusions.

The sulfur content of the first product is about 0.2 per cent, while the proportion of sulfur in the second product is about 0.4 per cent. This minute proportion of sulfur probably exists as sulfuric acid or sulfates whose absolutely complete removal has not been effected.

Havin now fully described my invention, what I c aim and desire to protect by Let ters Patent is:

1. As a new product, the herein described derivative from mineral oil, the same being a liquid, insoluble in water, practicaly odorless, which does not become rancid and containing a minute percentage of sulfur less than one per cent, the same also being readily saponifiable and when saponified being soluble in all proportions with water and mineral oil and adapted to undergo th character of hydrolytic decomposition that occurs with soaps derived from animal and vegetable oil.

2. As a new product, the herein described saponified derivative from mineral oil, the same being miscible in all proportions with water or mineral oil, adapted to undergo the character of hydrolytic decomposition that occurs with soaps of animal or vegetable origin and distinguishable from such soaps in that it contains a small proportion of sulfur not exceeding one per cent.

In testimony of which invention, I have hereunto set my hand, at Philadelphia, Pa., on this 28th day of March, 1919.

HAROLD T. MAITLAND.

Certificate of Correction.

It is hereb certified that in Letters Patent No. 1,425,884, granted Au st 15, 1922, u n t e application of Harold T. Maitland, of Marcus Hook, ennsylvania, or an improvement in Mineral-Oil Derivatives, an error appears in the printed specification requiring correction as follows: Page 3, line 41, beginning with the word Both strike out all to and inc'ludi the word effected in line 62; and that the said Letters Patent should be re with this correction therein that the same ma conform to the record of the case in the Patent Oflice.

Signed and se ed this 3d day of April, A. D., 1923.

[m] KARL FENNING,

Acting Uomma'anoner of Patents. 

